Contents lists available at ScienceDirect ELSEVIER Food Chemistry journal homepage: www.elsevier.com/locate/foodehem Analytical Methods Detection of coffee flavour ageing by solid-phase microextraction/surface acoustic wave sensor array technique (SPME/SAW) Nicole Barié’, Mark Bi ing'', Ullrich Stahl’, Michael Rapp ” 2s nit of Tecolgy (KI) tate for Mxracar Tahal (IST Hermanson at 1, 716344 Eeensti-eopoliafn, Germany Frmnkfr ns or Meal ilgy ant Ape Eley (ME) 37382 scale. Germany Peta de ger imi nr Cena el Eco, Que, Eundor ARTICLE INFO ABSTRACT Received 17 Jy 2013 Received i eed frm 3 September 2014 ‘Aetepte 11 Decere 2014 ‘alate anne 17 Becembes 2014 “The use of polymer coated surface acoustic wave (SAW) sensor arays i avery promising technique for highly sensitive and selective detection of volatile organic compounds (VOCS)-We present new develop. ments to achieves low cost sensor setup with sampling method enabling the highly reproducible detec tion of volatiles even in the pp range, Since the VOCs of eafee are wellknown by gas chromatography (Ge) research studies, the new sensor aay Was tasted foran easy assessable objective: coffe ageing dur- ing storage, As reference method these changes were traced with 3 tandard GCJFD set-up, accompanied erm by sensory panellists The evaluation of GC data showed a now-linear characteristic for single compound leans COncenttatons as welas fo otal peak area values, dabling prediction of the colle age In conta the Bree few SAW sensor aay demonstites a neat dependency, 4. being expable fo show 2 dependency Pg teteen vale concentration and storge tine. © 2014 Eleevier Ld, Al rights reserved, 1. Introduction {in soutine analysis wet chemical methods are often used for the determination of food quality. In addition instrumental methods and sensory analysis are described as usable toals for the determi- nation of the storage period, the quality and the origin, Unfortu nately, apatt from the time-consuming aspect of these methods, they are sensitive 10 misinterpretation, In the last decade new devices, socalled “electronic noses", have been described inthe li erature asa both cost-effective and timesaving substitute for these methods. Most of these chemical sensors showed deficiencies in selectivity, sensitivity and reproducibility and only a few systems are classified to partly replace the classical methods (cI Haugen, & Steinhart, 2003), ‘The aim of the present investigation was to study the analytical ‘capability of a new system which combines Solid Phase Micro [Extraction (SPME) with a newly developed Surface Acoustic Wave (SAW) based sensor system. The combination of a headspace utosampler with sample injection via SPME fibre is frequentiy, tused as a sampling method in classical gas chromatography (GC). ‘The latter of course involves a proper detector unit at the column, “F Comespnding tho. e: +89 721 6823258 fx 949 721 S082 G57, mal abies nichclppok eM. RAD. ‘shees145)0 2014 Evie Ud ih reseed ‘output as well Instead of using an expensive and a relatively slow GC plus attached detector, this study uses a self developed minia- turised sensor array based on eight differently coated SAW devices as detection unit. ince such sensors provide some semi-selectiv- ity, the necessity ofa laborious and time intensive GC separation, ‘can be omitted. SAW devices have already proved to be suitable in many technical applications, above all in electronics, electronic ‘data processing, and high-frequency technology. They have the advantages of being low-cost, simple in handling and are small, Sized, Typically, they are operated at an ultrasonic range of fie~ ‘quencies from 10 MHz to 2 GH Sensors on the basis of various different acoustic wave types, which differ in terms of boundary Conditions and the direction oftheir deflection components, have been already implemented for detection purposes in gaseous as well as in liquid media, eg. quartz crystal microbalances (Salainshi, Mouruna, & Rorube, 1996), sensors based on Ray- leigh waves (Wohitien & Dessy, 1979), acoustic plate modes (Warun. Ricco, Niemery & Frye, 1989), transverse surface waves (Ges, Flory, Tom-Moy. & Solomon, 1992) and. Love waves (Kovacs, Vellekoop, Haves, bling, & Venema, 1994). For sensing, such devices were typically equipped with selective coatings Which interact with the ambient medium by physical absorption Installed Into an esillator circuit the sensors serve as the Frequency determining element. The interaction of the acoustica et fond Cherry 1762015) 212-218, ns wave with the surrounding, medium then causes the velocity and. amplitude of the wave to change, which is indicated by a change Inthe resonance frequency of the oscillator. Thus, changes in the ‘mass density, mechanical stiffness or viscosity can be monitored as a sensing Fesponse. However, the major measurement parame~ ter generally is the change in’ resonance frequency due to the change in mass, which results from the interaction between ana~ Iyte and sensitive coating, To achieve selectivity towards a certain analyte, several sensor devices must then be combined properly forming a sensor array. An array of polymer coated SAW sensors with each sensor having a different sensitive coating, combined with a suitable data processing, allows retrieving the qualitative as well as the quantitative composition ofthe volatiles of interest. ‘Therefore, itis a very promising technique for highly sensitive and selective organic gas detection and electronic nose applications. [New developments in the fabrication of SAW sensors, e.g, coatin andl sampling techniques, enable a highly reproducible detection, ‘of volatiles in the ppm and ppb range. In the past we already presented a novel concept to achieve a ‘miniaturized SAW sensor array comprising a dramatic reduction, ff sampling volume and inner surface area which minimises Fesponse time and unwanted memory effects (Vile hav Romoudls, Voigt, & Rapp, 2003; Rapp, Reibel, Voigt, Balzer 100), For an on-line control of VOC's this system showed already an excellent long-term stability in combination with good Feproduelbility and selectivity (Wess), Kuipers, Rapp. & keibe SPME as a sample preparation technique for extraction of organic compounds from complex samples was introduced by Arthur andl Pawliszyn in 1990 ("=0is2yo, 1997) and further devel- ‘pein 1993 as headspace-SPME (292,199). This method. can concentrate volatile and non-volatile compounds from liquid 128, and solid matrices for chromatographic analyses. ASPME unit, ‘comprises a narrow diameter fused silica fibre coated with a thin, sorbent phase; usually a polymeric material (eg. poly ‘dimethylsiloxane (PDMS), polyacrylate, and divinyl benzene), in some cases mixed with a solid adsorbent (e. porous carbon) ‘The fibre is attached to a stainless steel plunger, which moves the coated fibre within a protective needle. For extraction the fibre is exposed to the sample or its headspace. from which the analytes ‘are concentrated directly by adsorption on the sorbent phase. The ‘method integrates sampling, extraction, concentration, and sample introduction into the chromatography system in a single step and can be automated routinely. It provides lower detection limits than, ‘other techniques, and dramatically reduces sample preparation, time. The SPME technique has been described and validated for ‘numerous applications in several areas, including chemical, eni- ronmental, pharmaceutical, aroma, food, and natural products analysts (Pawtszyn, 1997, 1999; Pelusio el al. 1995; Snow & Shack 2002: Yang & Peppave, 1995), Coupling the automated SPME technique with a SAW based microarray should lead to a powerful, tool for a wide range of applications. Because ofits high commercial impactinthe food industry, coffee ‘was selected as food material fortis study. State ofthe art oncoffee analysis isthe use of SPME in conjunction with GC and mass spec trometry (MS) as detector unit (\spc2 185-190, oshonoe Hea K, Keo, DM, Beast Park P2005). Cofe ‘Some suited sais af compesian das alana 82) 710-705. do ‘vtrefaina 200807 054 Eu 2009 ats Mole ane studi coma a the University of Kars, Gasman. 1985 Sherecenee fer diploma she worked at the Forschung Hae in he iid of tsemars 04 PAD, seen 199 she abated het PhD As 8 posto. the worked inthe applcition dvopment for sand besenss Her Bes of Inerst nie mnosenng ith SAW devices an the development a re= Concentration infor gs senor aay Since 2008 she tween a 2 poke Iapape atthe tae of Miron Tecbeagy (RI) kare ste UF Tarnogy (othe ares of miro ard aos uted ol ses. Mark Backing sid fod chomisty a he University of Hams, Germany (where he eee edn Ste Paminstionn 1987 an Ms PMD a i995. om poate 001 he worked a seseuch sets the stl ir Qultatskherng mpi Hamre cesany Until 2004 he eas a vou researc soem aml fropet fader at fgrtectnolgy snd Food Innovations BV. Wageningen, The FRetherande since 2004 he He ofthe Depart for Ehime ari ond ‘Analyst Fauna IIE Schraleber, German His esa terest nlace Inde food sty fn detection methods a cromatowraphie race anane ari 20d Cumy 1762015) 212-218 ‘ten ta sted chemistry athe Fecal University of arse, Germany Hveconed the PhO, degree 1999, During his PAD. shes tthe ste ft Irsromentl Ansa ofthe Frshungszentrum frlscuhe, Germany, he ssa fn meted to enhance te stabity of yay ns on SAW sensor well rw eoning techniques He worked st memo he RAD group SAW used ‘Sceuone nose Ateratee he Jn the BD group of anata! metal exe ‘nr a enor a te Ferschangzetun Kase Preset hes werk asa Poles nthe eles af ogaic and iermentt nail Chemistry 3 the Contra Unter of Edo Michael Rapp susie pysis in Start and Hsfetbee, Germany, where he {toned ht Diploma In 1947, Dring hae athe Unversity a Heber m6 ns company, Lideagshaen, he devnped SAW sears many for eran fue sear encore for NO, tection. 1981 eased ni PD dear and Fre Scene manager at aschuentim Karu, Germany, hee he ‘Sblised SAW sensor group developing several anaes SAW sensor stems Sra itp i earch prope vey sete pcre